溶胶-凝胶多孔二氧化硅减反膜稳定性研究

多孔SiO2膜层经热处理后，具有很高的激光破坏阈值，但是结构中有许多Si-OH亲水基团，导致光学透过率受环境相对湿度的影响很大。实验目的是改善膜层内部结构，使膜层结构中的亲水基团转变为疏水基团。提高膜层的疏水性，增强膜层的透过率稳定性。系统地研究了膜层透过率随时间变化的规律，在氨气和六甲基二硅氮烷(HMDS)混合气氛下热处理膜层，处理后生成Si-O-Si(CH2)3非极性疏水基团，使膜层的疏水性大大提高，因而膜层的透过率稳定性有大幅度提高。稳定性的提高延长了膜层的寿命。处理后膜层的表面粗糙度良好，均方根表面粗糙度(RMS)为3．575，平均粗糙度(RA)为2．850，能够满足大型激光器精密化发展的要求。     

疏水性SiO_2基减反膜稳定性研究

在SiO2溶胶合成阶段进行化学改性,将六甲基二硅氮烷(HMDS)引入SiO2溶胶,制得稳定的胶体,胶体中SiO2纳米颗粒表面的亲水性Si-OH基团被疏水性的Si-O-Si(CH3)3基团取代。采用旋转法在磷酸二氢钾(KDP)晶体表面涂膜,涂膜晶体峰值透射率99%以上。膜层光学均匀性良好,表面粗糙度均方根值为0.94 nm。膜层疏水性能好,水接触角达到140°。涂制疏水性SiO2基减反膜的KDP晶体无需热处理就具有较好的疏水防潮性能,与目前激光器使用的防潮减反双层膜相比,在室温高湿度条件下涂膜晶体透射率下降情况大致相当。旋转涂膜可以有效解决三倍频晶体入光面与出光面共3个波段需减反的问题。     

多孔性二氧化硅减反膜胶体规律性研究

溶胶凝胶法制备减反膜在高功率激光装置中有着重要运用,通过控制水与正硅酸乙酯(TEOS)不同物质的量之比制备不同粒径大小的二氧化硅悬胶体及二氧化硅减反膜,可以研究悬胶体粒径大小对溶液及膜层的激光破坏阈值、光学减反效率稳定性影响。结果表明制备获得的多孔性SiO2减反膜透射率均高于99.5%,激光破坏阈值均大于62J/cm2(1064nm,15ns),其中粒径小的SiO2减反膜透射率达到99.75%,激光破坏阈值高达77.42J/cm2(1064nm,15ns)。随着水酯物质的量比值增大,悬胶体溶液平均粒径增大,当水酯物质的量比值大于3.5时粒径增大幅度加快;粒径在10nm以下的溶液具有优异的稳定性,溶液颗粒大小、粘度等性能基本保持不变。在不同湿度环境下研究不同粒径膜层的稳定性,所有膜层在高湿度环境中透射率有所下降,其中大粒径膜层下降更明显,化学膜更适合在湿度低的环境下使用。     

高性能智能窗用掺钨二氧化钒膜系的研制

针对智能窗用的二氧化钒膜系需相变温度接近室温、红外调节率高、可见光透过率高等实际问题,通过薄膜设计(Coating designer,CODE)软件设计了一种由掺钨(Tungsten-doped,W-doped)二氧化钒(Vanadium dioxide,VO2)层和二氧化硅(Silicon dioxide,SiO2)减反层组成的高性能智能窗膜系。系统研究了各层膜的厚度对红外调节率和可见光透过率的影响,确定综合性能优良的膜系为玻璃/70nm掺钨二氧化钒/50nm二氧化硅,并采用大面积多靶磁控溅射系统制备出了该膜系。实验测得膜系的相变温度为38.2℃,红外调节率(2400 nm波长处)为40.4%,可见光的峰值透过率为46.3%。在太阳能红外波段,膜系具有良好的入射调节效果。此外,该膜系的制备方法与现有的大面积镀膜玻璃工艺兼容,适于工业化生产。     

一种具有多层ITO结构的高效屏蔽光学视窗

针对现有屏蔽光学视窗透过率低、表面反射率高的缺点,提出一种高效屏蔽光学视窗的设计方法。即将ITO材料作为光学介质的一种,采用匹配的多层膜设计原理,将多层ITO匹配到减反膜系中,通过用Madab语言对膜系进行仿真、优化,实现了反射率低于0．3％,透过率大于99％的光学性能,并通过特殊的结构把多层ITO连接在一起,实现高效电磁屏蔽性能。     

界面层对激光减反膜的影响研究

激光技术的发展对减反膜提出了超高透过率的要求,基板的表面特征在高精度减反膜的设计与制造中不可忽略.选择熔融石英为基板,Ta2O5和SiO2为高低折射率膜层材料,针对在0 °入射角下工作的532 nm激光减反膜进行设计与分析,得到膜层内的电场分布.在模拟计算中将基板的表面粗糙度等效为等比例混合膜,计算分析了理想设计条件下...     

有机物沉积质量对溶胶凝胶减反膜性能的影响规律

真空环境中高功率激光装置光学元件表面的有机物污染是限制其负载能力的原因之一。针对装置中常见的有机物污染和三倍频激光溶胶凝胶减反膜，通过精确控制真空环境中污染源的挥发扩散，制备了有机物质量面密度不同的元件表面，定量研究了有机污染物质量面密度对溶胶凝胶减反膜光学性能及损伤特性的影响规律。实验结果表明：样品表面粗糙度、透过率、损伤阈值等的变化量均与有机物质量面密度成正相关。有机污染物沉积量较少时，由于膜层孔隙被填充，膜层的表面粗糙度略有减小；随着沉积量增加，有机物附着影响表面形貌，粗糙度显著增加。溶胶凝胶减反膜在351 nm波长处的光学透过率随着有机物质量面密度的增加而逐渐降低，这与有机物分子改变溶胶凝胶膜孔隙填充比有关。样品表面的激光损伤阈值变化量和损伤面积随着有机物质量面密度的增加而增加，而且不同有机物沉积量的光学表面的损伤形貌存在显著差异。基于实验结果讨论了有机物影响溶胶凝胶减反膜性能的机理，并探讨了高功率激光系统的洁净度控制方法。     

离子源辅助红外探测器窗口减反膜的制备

硫化锌(ZnS)作为红外探测器窗口广泛地应用于红外技术中,为了提高ZnS在7~12 μm 使用波段的光学透过率和机械强度,选择YF₃和YbF₃两种红外低折射率膜料分别与ZnS进行匹配,设计并在离子源的辅助下制备出了两种该波段的红外减反膜,并进行了性能的对比。结果显示两种膜系在要求范围内都达到了平均90%的光学透过率,但是YF₃-ZnS减反膜的机械强度相比YbF₃-ZnS减反膜较差。     

脉冲磁控溅射制备树脂镜片红外防护功能薄膜

选取氮化硅和二氧化硅作为薄膜材料,借助膜系设计软件对膜系结构进行优化,采用中频脉冲磁控溅射技术进行薄膜制备.利用高反膜透射曲线拟合方法调整薄膜的实际沉积速率,减少膜厚控制误差,在树脂镜片CR39基底的凸面和凹面上分别镀制了符合设计要求的红外防护膜和可见光减反膜.镀膜后树脂镜片在420-680 nm的平均透过率大于95%...     

溶胶-凝胶法制备隔板玻璃三层减反膜

以钛酸正丁酯、正硅酸乙酯为前驱体,在薄膜设计软件的辅助下,采用溶胶-凝胶法在K9光学玻璃上制备了λ/4-λ/2-λ/2膜系宽带减反膜。该膜层的光学性能良好,在500～900 nm波长范围内的平均透过率为99.25%,透过率增益随入射角增加而增大,斜入射光入射角从0°增至60°仍能有效覆盖钕玻璃的主吸收峰,此时平均透过率增益从7.2%增至10.2%;在150℃下进行热处理后,膜层具有一定的耐擦拭性能,表面均匀性良好,均方根粗糙度为4.00 nm。     

Monodispersed Gold Nanorod‐Embedded Silica Particles as Novel Raman Labels for Biosensing

Biocompatible, photostable, and multiplexing‐compatible surface‐enhanced Raman spectroscopic tagging materials have been developed that are composed of gold nanorod (GNR)‐embedded silica particles and organic Raman labels. GNR‐embedded silica particles were prepared with different surface coverage by the assembly of GNRs on silica particles based on an electrostatic interaction and subsequent coating of silica with controllable thickness. This method allows the incorporation of various organic Raman labels to generate intense surface‐enhanced Raman scattering (SERS) spectra. Furthermore, SERS‐active particles are demonstrated as novel Raman tags for immunoassay. The results suggest SERS tags can be used for multiplex and ultrasensitive detection of biomolecules.     

Template‐Free Sol‐Gel Preparation of Superhydrophobic ORMOSIL Films for Double‐Wavelength Broadband Antireflective Coatings

A double‐layer double‐wavelength antireflective (AR) coating with 100% transmittance at both 1064 nm and 532 nm, which is very important in high power laser systems, is designed using thin film design software (TFCalc). The refractive indices for the bottom and top layers of the designed AR coating are about 1.30 and 1.14. A simple, template‐free sol‐gel route is proposed to prepare the superhydrophobic ORMOSIL (organically modified silicate) thin film, which has an ultralow refractive index, by silica particle surface modification using hexamethylisilazane (HMDS); this treatment decreases the refractive index of the silica thin film from 1.23 to 1.13. The formation mechanism of the ultralow refractive index thin film is proposed. The particle surface modification with HMDS significantly improves the hydrophobicity of the coated film; the water contact angle of the film increases from 23.4° to 160°. The bottom layer, which has a refractive index of 1.30, is prepared from acid‐catalyzed and base‐catalyzed mixed silica sol. A double‐layer silica AR coating is obtained with transmittances of 99.6% and 99.8% at 532 nm and 1064 nm, respectively.     

Brilliant Pitaya‐Type Silica Colloids with Central–Radial and High‐Density Quantum Dots Incorporation for Ultrasensitive Fluorescence Immunoassays

Creating secondary nanostructures from fundamental building blocks with simultaneous high loading capacity and well‐controlled size/uniformity, is highly desired for nanoscale synergism and integration of functional units. Here a novel strategy is reported for hydrophobic quantum dots (QDs) assembley with porous templates, to form pitaya‐type fluorescent silica colloids with densely packed and intact QDs throughout the silica matrix. The mercapto‐terminated dendritic silica spheres with highly accessible central–radial pores and metal‐affinity interior surface, are adopted as a powerful absorbent host for direct immobilization of QDs from organic phase with high loading capacity. The alkylsilane mediated silica encapsulation prevents QDs' optical degradation induced by ligand exchange and favors the homogeneous silica shell formation. These multiple QD embedded silica spheres exhibit good compatibility for different colored QDs with well‐preserved fluorescence, high colloidal/optical stability, and versatile surface functionality. It is demonstrated that after integration with a lateral flow strip platform, these silica colloids provide an ultrasensitive, specific, and robust immunoassay for C‐reaction protein in clinical samples as promising fluorescent reporters.     

钛宝石强激光负载的有机硅复合凝胶增透膜研究

以硅酸四乙酯(TEOS)和甲基三乙氧基硅烷(MTEOS)为前驱材料，用溶胶-凝胶(sol-gel)方法在钛宝石表面制备得到均匀性良好且具有高激光损伤阈值的有机硅复合凝胶增透膜。膜层在钛宝石激光器输出波段(750～850nm)的增透效果显著，其平均透过率超过98．6％；激光破坏阈值为2．2J／cm^2(800nm，300ps)；膜层表面均匀性达到激光波面的要求，在皮秒、飞秒超短脉冲高功率激光领域具有应用价值。溶胶的性能测试结果表明，溶胶粘度和成膜折射率均随溶液中CH3SiO1.5溶胶体含量的增加而增大，而膜层折射率受烘烤温度影响较小。     

Stable Encapsulation of QD Barcodes with Silica Shells

Quantum dot-doped mesoporous microbeads (QDMMs) are encapsulated with silica shells for enhanced chemical stability. The results show that a micro-emulsion procedure is highly efficient in coating QDMMs with polyvinyl alcohol (PVA), which is important in the subsequent deposition of a silica shell. Incorporation of fluorescent silane precursors allows direct observation of silica shells by fluorescence microscopy. The resulting silica coated QDMMs (QDMM@SiO(2)) exhibit remarkable stability against solvent-induced QD leaching and chemical-induced fluorescence quenching compared with uncoated QDMMs. Further development of this technology such as optimization of silica shell thickness, surface modification with non-fouling polymers, and conjugation with biomolecular probes will enable clinical translation of the optical barcoding technology for highly multiplexed detection and screening of genes and proteins.     

Polymer‐Based Organic Field‐Effect Transistors with Active Layers Aligned by Highly Hydrophobic Nanogrooved Surfaces

In this study, polymer‐based organic field‐effect transistors (OFETs) that exhibit alignment‐induced mobility enhancement, very small device‐to‐device variation, and high operational stability are successfully fabricated by a simple coating method of semiconductor solutions on highly hydrophobic nanogrooved surfaces. The highly hydrophobic nanogrooved surfaces (water contact angle >110°) are effective at inducing unidirectional alignment of polymer backbone structures with edge‐on orientation and are advantageous for realizing high operational stability because of their water‐repellent nature. The dewetting of the semiconductor solution is a critical problem in the thin film formation on highly hydrophobic surfaces. Dewetting during spin coating is suppressed by surrounding the hydrophobic regions with hydrophilic ones under appropriate designs. For the OFET array with an aligned terrace‐phase active layer of poly(2,5‐bis(3‐hexadecylthiophene‐2‐yl)thieno[3,2‐b]thiophene), the hole mobility in the saturation regime of 30 OFETs with channel current direction parallel to the nanogrooves is 0.513 ± 0.018 cm² V^?1 s^?1, which is approximately double that of the OFETs without nanogrooves, and the intrinsic operational stability is comparable to the operational stability of amorphous‐silicon field‐effect transistors. In other words, alignment‐induced mobility enhancement and high operational stability are successfully achieved with very small device‐to‐device variation. This coating method should be a promising means of fabricating high‐performance OFETs.     

One‐Pot Preparation of Conducting Polymer‐Coated Silica Particles: Model Highly Absorbing Aerosols

Near‐monodisperse 0.50 μm and 1.0 μm silica particles are surface‐modified using 3‐(trimethoxysilyl)propyl methacrylate (MPS) and subsequently coated by aqueous deposition of an ultrathin polypyrrole (PPy) overlayer to produce PPy‐coated silica particles. The targeted degree of MPS modification and PPy mass loading are systematically varied to optimize the colloidal stability and PPy coating uniformity. MPS surface modification is characterized by contact angle goniometry and the PPy overlayer uniformity is assessed by scanning electron microscopy. HF etching of the silica cores produces hollow PPy shells, thus confirming the contiguous nature of the PPy overlayer and the core–shell morphology of the original particles. Four‐point probe measurements and XPS studies indicate that the electrical conductivity of pressed pellets of PPy‐coated silica particles increases with PPy surface coverage. Colloidal stabilities of the bare, MPS‐modified, and PPy‐coated silica particles in aqueous solution are assessed using disk centrifuge photosedimentometry. MPS surface modification results in weak flocculation, with subsequent PPy deposition causing further aggregation. In contrast, white light aerosol spectrometry indicates a relatively high degree of dispersion for PPy‐coated silica particles in the gas phase. Such PPy‐coated silica particles are expected to be useful mimics for silica‐rich micrometeorites and may also serve as a model highly absorbing aerosol.     

Silica nanoparticle-embedded sol-gel organic/inorganic hybrid nanocomposite for transparent OLED encapsulation

We report a transparent moisture barrier coating fabricated with a silica nanoparticle-embedded organic/inorganic hybrid (S-H) nanocomposite. We used a photo-curable, cyclo-aliphatic epoxy based hybrid material (hyrimer) as the matrix and a solvent-less, monodisperse silica nanoparticles as the reinforcement responsible for creating tortuous diffusive path for moisture penetrants. The S-H nanocomposite barrier coating exhibits a single layer WVTR of 0.24 g/m² day (Ca-test) and an optical transparency of 90% in the visible range. The performance of the barrier coating was also verified in an OLED lifetime measurement test, in which an OLED encapsulated with an S-H nanocomposite barrier coating showed significantly extended lifetime.     

Mesocellular Silica Foam as an Epoxy Polymer Reinforcing Agent

A new type of mechanically improved rubbery epoxy composite is demonstrated based on the use of a mesocellular silica foam, denoted MSU‐F, as the reinforcement agent. The silica exhibits a surface area of 540 m² g^–1, a cell size of 26.5 nm (14.9 nm window size) and a pore volume of 2.2 cm³ g^–1. Most notably, the silica foam particles readily disperse in the epoxy matrix without the need for an organic surface modifier or dispersing agent. Relative to the pristine polymer, the tensile modulus, strength, strain‐at‐break, and toughness for the mesocomposites are systematically enhanced at relatively low silica loading over the range 1–9 wt %. Moreover, all of these benefits are realized without a sacrifice in thermal stability or optical transparency of the polymer. The results demonstrate that silica in mesocellular foam form can provide polymer reinforcement far beyond the level realized for non‐porous silica or silica with small mesopores at the same weight loading.